JP2016078318A - Method for manufacturing resin molded article, method for manufacturing resin molded article with plated layer, and resin molded article with plated layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin molded article manufacturing method capable of forming a plated layer on the surface of a resin molded article without mixing an LDS (laser direct structuring) additive in a resin composition itself, and to provide a method for manufacturing a resin molded article with a plated layer, and a resin molded article with a plated layer.SOLUTION: In a method for manufacturing a resin molded article 1 with a plated layer 5, after insertion of a film made of a thermoplastic resin containing an LDS additive into a mold, a thermoplastic resin composition, which contains the same type of a thermoplastic resin as the thermoplastic resin, is injection-molded to obtain a resin molded article 1, laser 2 is applied to the resin molded article 1, and then plating treatment is performed.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a resin molded product capable of using a laser direct structuring (hereinafter sometimes referred to as “LDS”) technique capable of directly forming a plating on the surface of a resin molded product. Moreover, it is related with the manufacturing method of the resin molded product with a plating layer using the manufacturing method of the said resin molded product, and the resin molded product with a plating layer.

  In recent years, with the development of mobile phones including smartphones, various methods for manufacturing antennas inside mobile phones have been studied. In particular, there is a need for a method of manufacturing an antenna that can be three-dimensionally designed for a mobile phone. As one of the techniques for forming such a three-dimensional antenna, the LDS technique has attracted attention. LDS technology, for example, irradiates the surface of a resin molded product containing an LDS additive with a laser, activates only the portion irradiated with the laser, and forms a plating layer by applying metal to the activated portion. Technology. A feature of this technique is that a metal structure such as an antenna can be manufactured directly on the surface of the resin base material without using an adhesive or the like. Such LDS technology is disclosed in Patent Documents 1 to 4, for example.

Special table 2000-503817 Special table 2004-534408 gazette International Publication WO2009 / 141800 Pamphlet International Publication WO2012 / 128219 Pamphlet

Here, in adopting the LDS technique, it is conceivable to add an LDS additive to a thermoplastic resin composition for producing a resin molded product. However, when an LDS additive is added to the thermoplastic resin composition, a large amount of LDS additive is required. In addition, the LDS additive is necessary for forming the plating layer, but is not necessary for maintaining the function (for example, mechanical strength and flame retardancy) of the resin molded product itself. Rather, other components may be damaged by the LDS additive or the desired characteristics may not be exhibited.
An object of the present invention is to solve the above-mentioned problems, and is a method for producing a resin molded article using a thermoplastic resin composition, and an LDS additive is added to the thermoplastic resin composition itself. The present invention relates to a method for producing a resin molded product capable of forming a plating layer on the surface of the resin molded product without blending. Furthermore, it is related with the manufacturing method of the resin molded product with a plating layer, and the resin molded product with a plating layer.

As a result of intensive studies by the present inventors under the above-mentioned problems, a film containing a thermoplastic resin and an LDS additive and a thermoplastic resin composition containing the same thermoplastic resin as the thermoplastic resin are thermoformed. As a result, it has been found that the above problems can be solved, and the present invention has been solved.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <8>.
<1> A method for producing a resin molded article, comprising thermoforming a thermoplastic resin composition containing a thermoplastic resin and a laser direct structuring additive, and a thermoplastic resin of the same type as the thermoplastic resin. .
<2> The method for producing a resin molded article according to <1>, comprising injection-molding or in-mold molding the thermoplastic resin composition into a metal mold provided with the film.
<3> The method for producing a resin molded article according to <1> or <2>, wherein the thermoplastic resin composition contains inorganic fibers.
<4> The method for producing a resin molded product according to <3>, wherein the inorganic fiber is a glass fiber.
<5> The method for producing a resin molded product according to any one of <1> to <4>, wherein the film and the thermoplastic resin composition each contain a polyamide resin.
<6> The surface of the resin molded product manufactured by the method for manufacturing a resin molded product according to any one of <1> to <5> is further irradiated with a laser, and then a metal is applied to form a plating layer. The manufacturing method of the resin molded product with a plating layer including this.
<7> The method for producing a resin molded article with a plating layer according to <6>, wherein the plating layer contains copper.
<8> A resin molded product with a plated layer obtained by the method for producing a resin molded product with a plated layer according to <6> or <7>.

  According to the present invention, there is provided a method for producing a resin molded product using a thermoplastic resin composition, wherein a plating layer is formed on the surface of the resin molded product without adding an LDS additive to the thermoplastic resin composition itself. It has become possible to provide a method for producing a moldable resin molded product. Furthermore, it is possible to provide a method for producing a resin molded product with a plated layer and a resin molded product with a plated layer.

It is the schematic which shows the process of providing plating on the surface of a resin molded product.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

The method for producing a resin molded product of the present invention includes a film containing a thermoplastic resin and a laser direct structuring additive (hereinafter, sometimes referred to as “LDS additive-containing thermoplastic resin film”) and the thermoplastic resin. A thermoplastic resin composition containing a series of thermoplastic resins is thermoformed. By setting it as such a structure, it becomes possible to provide the resin molded product which can form a plating layer on the surface of a resin molded product, even if it does not mix | blend an LDS additive with thermoplastic resin composition itself.
Moreover, since the resin of the same system is used for the LDS additive-containing thermoplastic resin film and the thermoplastic resin composition, the adhesion between the LDS additive-containing thermoplastic resin film and the thermoplastic resin composition can be increased.
In addition, in the present invention, since the LDS additive-containing thermoplastic resin film and the thermoplastic resin composition are thermoformed, the LDS additive is present only in the vicinity of the surface layer of the resin molded product, not the entire resin molded product. Can be configured. As a result, a good plating layer can be formed even if the amount of the LDS additive is small relative to the entire resin molded product. The LDS additive itself acts as a foreign substance in the resin molded product and reduces the mechanical strength and the like. However, in the present invention, since the ratio of the LDS additive to the resin molded product is relatively small, the mechanical strength and the like are reduced. Can be more effectively suppressed.

<Thermoplastic resin film containing LDS additive>
The LDS additive-containing thermoplastic resin film used in the present invention contains a thermoplastic resin and an LDS additive.
<< Thermoplastic resin >>
Examples of the thermoplastic resin used in the present invention include alloys of polyphenylene ether resin and polystyrene resin, alloys of polyphenylene ether resin and polyamide resin, thermoplastic polyester resin, methyl methacrylate / acrylonitrile / butadiene / styrene copolymer resin, methyl methacrylate. / Styrene copolymer resin, methyl methacrylate resin, rubber-reinforced methyl methacrylate resin, polyamide resin, polyacetal resin, polyurethane resin, polylactic acid resin, polyolefin resin, polyphenylene sulfide resin and the like. In this invention, it is preferable that at least 1 sort (s) of a thermoplastic polyester resin and a polyamide resin is included, and it is further more preferable that a polyamide resin is included.
The thermoplastic resin composition used in the present invention may contain only one type of resin, or may contain two or more types.

Embodiment with Polyamide Resin as Main Component When the thermoplastic resin composition in the present invention contains a polyamide resin, the polyamide resin is more preferably contained in an amount of 50% by weight or more, more preferably 60% by weight or more, 70 More preferably, it is contained in an amount of 80% by weight or more. The upper limit when the thermoplastic resin includes a polyamide resin is 100% by weight or less.

Polyamide resin The polyamide resin is a polymer having a repeating unit of acid amide obtained by ring-opening polymerization of lactam, polycondensation of aminocarboxylic acid, and polycondensation of diamine and dibasic acid. Specifically, polyamide 6 11, 12, 46, 66, 610, 612, 6I, 6/66, 6T / 6I, 6 / 6T, 66 / 6T, 66 / 6T / 6I, polyamide MX, polytrimethylhexamethylene terephthalamide, polybis (4 -Aminocyclohexyl) methane dodecamide, polybis (3-methyl-4-aminocyclohexyl) methane dodecamide, polyundecamethylene hexahydroterephthalamide and the like. In addition, said "I" shows an isophthalic acid component and "T" shows a terephthalic acid component.
As the polyamide resin used in the present invention, an appropriate polyamide resin is selected in consideration of various properties of these polyamide resins and the intended use of the molded product.

Among the above-mentioned polyamide resins, the semi-aromatic polyamide resin having an aromatic ring as a raw material dicarboxylic acid component, the polyamide MX resin having an aromatic ring as a raw material diamine component, or a polyamide resin mixed with these is a glass that increases strength. A compound containing a relatively large amount of fillers such as fibers and carbon fibers can be easily obtained, which is preferable.
Specific examples of the semi-aromatic polyamide include 6I, 6T / 6I, 6 / 6T, 66 / 6T, 66 / 6T / 6I, and the like.
Further, the polyamide MX resin is preferably obtained by polycondensation of xylylenediamine and α, ω-dibasic acid, and paraxylylenediamine and / or metaxylylenediamine and α, ω having 6 to 12 carbon atoms. -Polyamide resin obtained by polycondensation of linear aliphatic dibasic acid or aromatic dibasic acid, particularly preferably paraxylylenediamine and / or metaxylylenediamine, sebacic acid and / or adipic acid. It is the polyamide MX resin used. Moreover, as a copolymerization component, diamine, dicarboxylic acid, etc. generally used with polyamide resin, such as T, I, and bisaminomethylcyclohexane, can be used.
A mixture of a polyamide resin having an aromatic ring and an aliphatic polyamide resin (for example, polyamide 6, polyamide 66, etc.) is also preferably used. Even when the aliphatic polyamide resin alone is blended with a large amount of filler, the appearance and physical properties are improved by mixing with the above polyamide resin having an aromatic ring even when the appearance and physical properties are not sufficient. In the case of a mixture of a polyamide resin having an aromatic ring and an aliphatic polyamide resin, the weight ratio is preferably 100: 1 to 100: 40.

Embodiment with Thermoplastic Polyester Resin as Main Component As an embodiment of the thermoplastic resin in the present invention, a case where the thermoplastic resin contains a thermoplastic polyester resin as a main component can be mentioned. In the present embodiment, the ratio of the thermoplastic polyester resin in all resin components is preferably 51 to 100% by weight, more preferably 80 to 100% by weight, and further preferably 90 to 100% by weight.

Thermoplastic polyester resin As the thermoplastic polyester resin, the description of paragraph numbers 0013 to 0016 of JP 2010-174223 A can be referred to.
As the polyester resin, a polybutylene terephthalate resin or a mixture containing 60% by weight or more, preferably 80% by weight or more of polybutylene terephthalate resin is usually used. For example, when a mixture of a polybutylene terephthalate resin and a polyethylene terephthalate resin is used, one having a ratio of 60 to 95% by weight, more preferably 70 to 90% by weight, is preferable as the polyester resin used in the present invention. It is.
As is well known, polybutylene terephthalate resin and polyethylene terephthalate resin are produced on a large scale by reaction of terephthalic acid or its ester with 1,4-butanediol or ethylene glycol, and are distributed in the market. In the present invention, these resins available on the market can be used. Some commercially available resins contain a copolymer component other than a terephthalic acid component and a 1,4-butanediol component or an ethylene glycol component. However, in the present invention, a small amount of a copolymer component is usually used. Those containing 20% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less can be used. When the copolymer component is contained, isophthalic acid, polytetramethylene glycol, and dimer acid are preferably used as the copolymer component.
The intrinsic viscosity of the polybutylene terephthalate resin is usually 0.5 to 1.5 dl / g, particularly preferably 0.6 to 1.3 dl / g. If it is less than 0.5 dl / g, it is difficult to obtain a resin composition having excellent mechanical strength. On the other hand, if it is larger than 1.5 dl / g, the fluidity of the resin composition is lowered, and the moldability may be lowered. Moreover, it is preferable that the amount of terminal carboxyl groups is 30 meq / g or less. Furthermore, the content of tetrahydrofuran derived from 1,4-butanediol is preferably 300 ppm or less.
Further, the intrinsic viscosity of the polyethylene terephthalate resin is usually 0.4 to 1.5 dl / g, and particularly preferably 0.5 to 1.3 dl / g. If the intrinsic viscosity is less than 0.4 dl / g, the mechanical properties of the resin composition are likely to be lowered, and if it exceeds 1.5 dl / g, the fluidity is liable to be lowered. In addition, any intrinsic viscosity is a measured value in 30 degreeC in a phenol / tetrachloroethane (weight ratio 1/1) mixed solvent.
The thermoplastic resin composition used in the present invention may contain only one kind of thermoplastic polyester resin, or may contain two or more kinds.
In the present embodiment, a resin component other than the thermoplastic polyester resin may be included. However, the other resin is preferably 5% by weight or less of the total resin components.

  In addition, the details of the thermoplastic resin can be referred to the descriptions in paragraphs 0011 to 0028 of JP 2014-074162 A, and the contents thereof are incorporated in the present specification.

  The content of the thermoplastic resin in the LDS additive-containing thermoplastic resin film is preferably 20 to 98% by weight, and more preferably 70 to 95% by weight. Only one type of thermoplastic resin may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range. In particular, the ratio of the resin of the same system as the resin contained in the resin composition to be described later is preferably 60% by weight or more among all thermoplastic resins contained in the LDS additive-containing thermoplastic resin film, and 80% by weight. % Or more is more preferable. By setting it as such a range, the effect of this invention is exhibited more effectively. In addition, even when outside the above range, if the matrix (sea part of the sea-island structure) is the same in the morphology, the effect is sufficiently exerted.

<< Laser direct structuring additive >>
The LDS additive-containing thermoplastic resin film in the present invention contains an LDS additive.
The LDS additive in the present invention is based on 100 parts by weight of MP6 (MP6 synthesized in Examples described later), 4 parts by weight of an additive considered to be an LDS additive is added, and a YAG laser having a wavelength of 1064 nm is used. Irradiate at an output of 10W, a frequency of 80kHz, and a speed of 3m / s, and the subsequent plating process was performed in an electroless MacDermid M-Copper85 plating tank, and plating was performed when metal was applied to the laser irradiated surface. A compound that can be formed. For example, if an additive is added to the resin, the absorption of the YAG laser is poor and the surface of the resin cannot be burned cleanly. In order to burn the surface with the laser, 10 to 40 parts by weight of titanium oxide is added and evaluated. Also good.
The LDS additive used in the present invention may be a synthetic product or a commercial product. Moreover, as long as the commercially available product satisfies the requirements for the LDS additive in the present invention, it may be a material sold for other uses as well as those marketed as LDS additives.

The blending amount of the LDS additive in the LDS additive-containing thermoplastic resin film is preferably 3 to 20 parts by weight, more preferably 5 to 20 parts by weight, and further preferably 100 parts by weight of the thermoplastic resin. Is 8 to 20 parts by weight.
Only one type of LDS additive may be used, or two or more types may be used in combination. When using 2 or more types, it is preferable that the total amount becomes the said range.

  Hereinafter, preferred embodiments of the LDS additive used in the present invention will be described. By using the LDS additive of such an embodiment, the effects of the present invention tend to be more effectively exhibited. However, it goes without saying that the present invention is not limited to these embodiments.

  The LDS additive of the first embodiment used in the present invention is in a form containing at least one of antimony and tin. The LDS additive of the first embodiment more preferably contains antimony and tin, more preferably contains antimony and tin, more preferably contains more tin than antimony, contains antimony and tin oxide, It is particularly preferable that the content of tin is higher than that of antimony. Moreover, the aspect which contains an antimony oxide and a tin oxide and tin has more content than an antimony is illustrated preferably. In the present embodiment, it is preferable that 80% by weight or more of the metal component is tin. The LDS additive of the first embodiment can be an LDS additive having a reflectance of 50% or more at a wavelength of 450 nm.

The LDS additive of the second embodiment used in the present invention is an LDS additive containing copper. The LDS additive used in the second embodiment is preferably an oxide containing copper, and more preferably an oxide containing copper and chromium (copper chromium oxide). Examples of such an LDS additive include CuCr ₂ O ₄ and Cu ₃ (PO ₄ ) ₂ Cu (OH) ₂ , and CuCr ₂ O ₄ is particularly preferable. Thus, the effect of the present invention tends to be exhibited more effectively by using an oxide containing copper as an LDS additive. The LDS additive of the second embodiment preferably has a spinel structure. The copper content in the LDS additive used in the second embodiment is preferably 20 to 95% by weight.

Moreover, the LDS additive of the said 1st Embodiment and 2nd Embodiment, and the LDS additive of 4th Embodiment mentioned later, the composition containing the said LDS additive, some base-material surface, A part or the whole may be coated. By setting it as such a structure, the ratio which the composition containing a LDS additive comes out on the surface increases, and it becomes possible to exhibit a high LDS effect even with a small amount of LDS additive. Further, by adopting a composition having a reflectance of 50% or more for the composition constituting the center part, it becomes possible to increase the reflectance of the obtained thermoplastic resin molded article.
The composition constituting the central part preferably contains a metal oxide, and more preferably contains at least one of silicon dioxide, mica, titanium oxide and zinc oxide.

The LDS additive used in the third embodiment of the present invention is an LDS additive having a reflectance of 50% or more at a wavelength of 450 nm. By adopting such an LDS additive, the reflectance of the obtained thermoplastic resin molded article can be increased.
As a specific example of such an LDS additive, a composition containing at least one of an oxide containing copper and an oxide containing tin and antimony on the surface of a composition having a reflectance of 50% or more at a wavelength of 450 nm. The thing by which the thing is coated is illustrated. More preferably, a composition having a reflectivity of 50% or more in the center is coated with a composition containing at least one of copper, tin and antimony in an area of 60% or more of the surface area of the center. is there. The composition constituting the central part preferably contains a metal oxide, more preferably contains at least one of silicon dioxide, titanium oxide, and zinc oxide, and more preferably contains titanium oxide and zinc oxide. .
Further, as another specific example of the LDS additive having a reflectance at a wavelength of 450 nm of 50% or more, an LDS additive having a high reflectance (for example, the above-mentioned) is added to the surface of the composition having a reflectance at a wavelength of 450 nm of less than 50%. LDS additive coated with a composition containing the LDS additive of the first embodiment). Examples of the composition having a reflectance of less than 50% at a wavelength of 450 nm include mica.

The LDS additive used in the fourth embodiment of the present invention preferably contains at least two metals and a conductive oxide having a resistivity of 5 × 10 ³ Ω · cm or less. The resistivity of the conductive oxide is preferably 8 × 10 ² Ω · cm or less, more preferably 7 × 10 ² Ω · cm or less, and further preferably 5 × 10 ² Ω · cm or less. Although there is no restriction | limiting in particular about a minimum, For example, it can be set to 1 * 10 < ¹ > ohm * cm or more, Furthermore, it can be set to 1 * 10 < ² > ohm * cm or more.
The resistivity of the conductive oxide in the present invention generally refers to the powder resistivity, and 10 g of the fine powder of the conductive oxide is loaded into a cylinder having an inner diameter of 25 mm and having an inner surface subjected to Teflon processing (Teflon: registered trademark). Then, the pressure can be increased to 100 kg / cm ² (20% filling rate), and measurement can be performed with a “3223 type” tester manufactured by Yokogawa Electric Corporation.

The LDS additive used in the fourth embodiment is not particularly limited as long as it contains a conductive oxide having a resistivity of 5 × 10 ³ Ω · cm or less, but preferably contains at least two kinds of metals. Specifically, it preferably contains a metal of group n (n is an integer of 3 to 16) and a metal of group n + 1 of the periodic table. n is preferably an integer of 10 to 13, more preferably 12 or 13.
In the LDS additive, the LDS additive used in the fourth embodiment is 100 mol in total of the content of the group n metal (n is an integer of 3 to 16) and the metal content of the n + 1 group in the periodic table. %, The content of one metal is preferably 15 mol% or less, more preferably 12 mol% or less, and particularly preferably 10 mol% or less. Although there is no restriction | limiting in particular about a minimum, It is 0.0001 mol% or more. By setting the content of two or more kinds of metals in such a range, the plating property can be improved. In the present invention, an n group metal oxide doped with an n + 1 group metal is particularly preferable.
Further, in the LDS additive used in the fourth embodiment, 98% by weight or more of the metal component contained in the LDS additive is composed of the group n metal content and the group n + 1 metal of the periodic table. It is preferable.

  Examples of the metal of group n in the periodic table include group 3 (scandium, yttrium), group 4 (titanium, zirconium, etc.), group 5 (vanadium, niobium, etc.), group 6 (chromium, molybdenum, etc.), group 7 ( Manganese, etc.), group 8 (iron, ruthenium, etc.), group 9 (cobalt, rhodium, iridium, etc.), group 10 (nickel, palladium, platinum), group 11 (same, silver, gold, etc.), group 12 (zinc, Cadmium, etc.), group 13 (aluminum, gallium, indium, etc.), group 14 (germanium, tin, etc.), group 15 (arsenic, antimony, etc.), group 16 (selenium, tellurium, etc.), and metal oxides thereof. It is done. Among them, a Group 12 (n = 12) metal or metal oxide is preferable, and zinc is more preferable.

  Examples of the metal of group n + 1 of the periodic table include group 4 (titanium, zirconium, etc.), group 5 (vanadium, niobium, etc.), group 6 (chromium, molybdenum, etc.), group 7 (manganese, etc.), group 8 (iron). , Ruthenium, etc.), group 9 (cobalt, rhodium, iridium, etc.), group 10 (nickel, palladium, platinum), group 11 (same, silver, gold, etc.), group 12 (zinc, cadmium, etc.), group 13 (aluminum) Gallium, indium, etc.), group 14 (germanium, tin, etc.), group 15 (arsenic, antimony, etc.), group 16 (selenium, tellurium, etc.), and metal oxides thereof. Among them, a Group 13 (n + 1 = 13) metal or metal oxide is preferable, aluminum or gallium is more preferable, and aluminum is further preferable.

The LDS additive used in the fourth embodiment may contain a metal other than the conductive metal oxide. Examples of the metal other than the conductive oxide include antimony, titanium, indium, iron, cobalt, nickel, cadmium, silver, bismuth, arsenic, manganese, chromium, magnesium, and calcium. These metals may exist as oxides. The content of these metals is preferably 0.01% by weight or less with respect to the LDS additive.
The LDS additive used in the fourth embodiment has an antimony content of preferably 3% by weight or less and preferably 1% by weight or less with respect to the LDS additive from the viewpoint of improving the L value. More preferably, it is more preferable that it is 0.01 weight% or less, and it is especially preferable not to contain substantially. “Substantially free” means not contained within a range that affects the effects of the present invention.

  The LDS additive used in the fourth embodiment is preferably capable of absorbing light having a wavelength of 1064 nm. By making it possible to absorb light having a wavelength of 1064 nm, it is easy to form a plating layer on the surface of the resin molded product.

  The particle diameter of the LDS additive used in the fourth embodiment is preferably 0.01 to 50 μm, and more preferably 0.05 to 30 μm. By adopting such a configuration, the uniformity of the plating surface state tends to be good when plating is applied.

<< other ingredients >>
The LDS additive-containing thermoplastic resin film used in the present invention may contain other components without departing from the spirit of the present invention. Other components include elastomers, talc, mold release agents, antioxidants, heat stabilizers and other stabilizers, hydrolysis resistance improvers, weathering stabilizers, matting agents, UV absorbers, nucleating agents, plasticizers In addition, additives such as a dispersant, a flame retardant, an antistatic agent, an anti-coloring agent, an anti-gelling agent, a coloring agent, and a release agent can be added. Details of these can be referred to the description of paragraph numbers 0130 to 0155 of Japanese Patent No. 4894982, the contents of which are incorporated herein. Moreover, about an elastomer, a talc, and a mold release agent, these description in the thermoplastic resin composition mentioned later can be referred and the preferable range is also synonymous.
These components are preferably 20% by weight or less of the LDS additive-containing thermoplastic resin film.

<Thermoplastic resin composition>
The thermoplastic resin composition in the present invention contains a thermoplastic resin of the same system as the LDS additive-containing thermoplastic resin film. The same series of thermoplastic resins include, for example, polyamide resins, polyester resins, polyolefin resins, polypropylene resins, polyethylene resins, acrylic resins, polyacetal resins, polycarbonate resins, styrene resins, and polyamide resins. Examples include combinations of polyurethane resins. In the present invention, the LDS additive-containing thermoplastic resin film and the thermoplastic resin composition preferably each contain a polyamide resin.
In the present invention, the same resin may be included in the thermoplastic resin composition and the LDS additive-containing thermoplastic resin film as the resin of the same system, or different resins may be included in the same system. .
In this invention, it is preferable that the ratio of the thermoplastic resin of the said system | strain is 50 weight% or more in the resin component contained in a thermoplastic resin composition, and it is more preferable that it is 70 weight% or more. Moreover, the thermoplastic resin composition may contain two or more types of thermoplastic resins. In this case, it is preferable that the two or more kinds of resins are the same series of thermoplastic resins.
The blending amount of the thermoplastic resin in the thermoplastic resin composition may be 100% by weight, but may contain other components. When other components are included, the total amount of the thermoplastic resin in the thermoplastic resin composition is preferably 30% by weight or more, more preferably 35% by weight or more, and more preferably 35 to 70% by weight. More preferably.
The thermoplastic resin composition used in the present invention may contain an LDS additive, but can be configured so as not to contain substantially. “Substantially free” means, for example, 1% by weight or less of the total components of the thermoplastic resin composition.

<< Inorganic fiber >>
The thermoplastic resin composition preferably further contains inorganic fibers. By blending the inorganic fibers, the mechanical strength of the resin molded product can be improved. Moreover, dimensional accuracy can be improved more by mix | blending inorganic fiber. Only one type of inorganic fiber may be used, or two or more types may be used in combination.
Examples of inorganic fibers include glass fibers and carbon fibers, with glass fibers being preferred.

  The glass fiber preferably used in the present invention preferably has an average diameter of 20 μm or less, and further 3 to 18 μm further increases the balance of physical properties (strength, rigidity, heat-resistant rigidity, impact strength) and molding. This is preferable in that the warpage is further reduced. In general, glass fibers having a circular cross-sectional shape are generally used in many cases. However, in the present invention, there is no particular limitation. For example, a glass fiber having a cross-sectional shape of an eyebrow shape, an oval shape, or a rectangular shape can also be used.

  The length of the glass fiber is not specified and can be selected from a long fiber type (roving), a short fiber type (chopped strand), or the like. In this case, the number of focusing is preferably about 100 to 5000. If the length of the glass fiber in the composition after kneading the composition of the present invention is not less than a desired length (for example, an average fiber length of 0.1 mm or more), so-called milled fiber or glass powder is obtained. May be a pulverized product of strands referred to as a continuous sliver. The composition of the raw material glass is preferably non-alkali, and examples thereof include E glass, C glass, and S glass. In the present invention, E glass is preferably used.

  The glass fiber is preferably surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. The adhesion amount is usually 0.01 to 1% by weight of the glass fiber weight. Furthermore, if necessary, a lubricant such as a fatty acid amide compound, silicone oil, an antistatic agent such as a quaternary ammonium salt, a resin having a film forming ability such as an epoxy resin or a urethane resin, a resin having a film forming ability and a heat. What was surface-treated with a mixture of a stabilizer, a flame retardant, etc. can also be used.

In the thermoplastic resin composition, the amount of the inorganic fiber is preferably 10 to 150 parts by weight, more preferably 10 to 130 parts by weight, and still more preferably 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin. More than 100 parts by weight.
As one Embodiment of a thermoplastic resin composition, the aspect which occupies 60 weight% or more of all the components with a thermoplastic resin and inorganic fiber is mentioned.

<< Elastomer >>
The thermoplastic resin composition may further contain an elastomer. Thus, the impact resistance of a thermoplastic resin composition can be improved by containing an elastomer.

  The elastomer used in the present invention is preferably a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith. The production method of the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft.

  The rubber component usually has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber. Silicone rubber, butadiene-acrylic composite rubber, IPN (Interpenetrating Polymer Network) type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc. And ethylene-α-olefin rubber, ethylene-acrylic rubber, fluororubber, and the like. These may be used alone or in admixture of two or more. Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable. .

  Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

  The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred. The core / shell type graft copolymer preferably contains 40% by weight or more of rubber component, more preferably 60% by weight or more. Moreover, what contains 10 weight% or more of (meth) acrylic acid is preferable. The core / shell type in the present invention does not necessarily have to be clearly distinguishable between the core layer and the shell layer, and includes a wide range of compounds obtained by graft polymerization of a rubber component around the core portion. It is the purpose.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include a styrene copolymer, a methyl methacrylate- (acryl / silicone IPN rubber) copolymer, and a styrene-ethylene-butadiene-styrene copolymer. Such rubbery polymers may be used alone or in combination of two or more.

  When blended, the elastomer content in the thermoplastic resin composition is preferably 0.1 to 40% by weight, more preferably 0.5 to 25% by weight, and still more preferably 1 to 4% by weight of the total amount of the thermoplastic resin composition. 10% by weight.

<< Talc >>
The thermoplastic resin composition may further contain talc. By adding talc, dimensional stability and product appearance can be improved, and even if the amount of LDS additive is reduced, the plating property of the resin molded product can be improved. An appropriate plating can be formed. As the talc, one having a surface treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes may be used. In this case, the adhesion amount of the siloxane compound in talc is preferably 0.1 to 5% by weight of talc.

  When blended, the amount of talc in the thermoplastic resin composition is preferably 0.01 to 10 parts by weight, and 0.05 to 8 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition. It is more preferable that the amount is 0.5 to 5 parts by weight. Moreover, when the talc is surface-treated with a siloxane compound, the blending amount of the talc surface-treated with the siloxane compound is preferably within the above range.

<< Releasing agent >>
The thermoplastic resin composition may further contain a release agent. The mold release agent is mainly used for improving the productivity at the time of molding the thermoplastic resin composition. Examples of the release agent include aliphatic carboxylic acid amides, aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, polysiloxane silicone oils, and the like. Can be mentioned. Among these release agents, carboxylic acid amide compounds are particularly preferable.

  Examples of the aliphatic carboxylic acid amide system include compounds obtained by a dehydration reaction between a higher aliphatic monocarboxylic acid and / or a polybasic acid and a diamine.

  The higher aliphatic monocarboxylic acid is preferably a saturated aliphatic monocarboxylic acid or hydroxycarboxylic acid having 16 or more carbon atoms, and examples thereof include palmitic acid, stearic acid, behenic acid, montanic acid, and 12-hydroxystearic acid. .

  Examples of polybasic acids include aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid, and azelaic acid, aromatic dicarboxylic acids such as phthalic acid and terephthalic acid, cyclohexanedicarboxylic acid, and cyclohexylsuccinic acid. And alicyclic dicarboxylic acids such as acids.

  Examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, and isophoronediamine.

  As the carboxylic acid amide compound, a compound obtained by polycondensation of stearic acid, sebacic acid and ethylenediamine is preferable, and a compound obtained by polycondensation of 2 mol of stearic acid, 1 mol of sebacic acid and 2 mol of ethylenediamine is more preferable. In addition to bisamide compounds obtained by reacting diamines with aliphatic carboxylic acids such as N, N′-methylenebisstearic acid amide and N, N′-ethylene bisstearic acid amide, N, N′— Dicarboxylic acid amide compounds such as dioctadecyl terephthalic acid amide can also be suitably used.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerol monopalmitate, glycerol monostea Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. The number average molecular weight of the aliphatic hydrocarbon is preferably 5000 or less.

  The content of the release agent is usually 0.001 part by weight or more, preferably 0.01 part by weight with respect to 100 parts by weight in total of the thermoplastic resin and the glass fiber in the thermoplastic resin composition. In addition, it is usually 2 parts by weight or less, preferably 1.5 parts by weight or less. By making content of a mold release agent 0.001 weight part or more with respect to a total of 100 weight part of a thermoplastic resin and glass fiber, mold release property can be made favorable. Moreover, by making the content of the release agent 2 parts by weight or less with respect to a total of 100 parts by weight of the thermoplastic resin and the glass fiber, a decrease in hydrolysis resistance can be prevented, Mold contamination during injection molding can be prevented.

<< Other additives >>
The thermoplastic resin composition may further contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include pigments (titanium oxide, etc.), alkalis, heat stabilizers, flame retardants, light stabilizers, antioxidants, UV absorbers, dyes and pigments, fluorescent whitening agents, anti-dripping agents, and antistatic agents. Agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like. These components may use only 1 type and may use 2 or more types together.

<Method for producing thermoplastic resin composition>
Any method can be adopted as a method for producing the thermoplastic resin composition. For example, a method of mixing a thermoplastic resin, an LDS additive, and glass fiber using a mixing means such as a V-type blender, adjusting a batch blend, and then melt-kneading with a vented extruder to pelletize Is mentioned. Alternatively, as a two-stage kneading method, components other than glass fiber, etc., are mixed in advance and then melt-kneaded with a vented extruder to produce pellets, and then the pellets and glass fibers are mixed and then vented The method of melt-kneading with an extruder is mentioned.

Furthermore, components other than glass fiber, etc., which are sufficiently mixed with a V-type blender, etc. are prepared in advance, and this mixture is supplied from the first chute of the vented twin-screw extruder, and the glass fiber is in the middle of the extruder. A method of supplying from the second chute and melt-kneading and pelletizing can be mentioned.
As for the screw configuration of the kneading zone of the extruder, it is preferable that the element that promotes kneading is arranged on the upstream side, and the element having a boosting ability is arranged on the downstream side.

  Examples of elements that promote kneading include a progressive kneading disk element, an orthogonal kneading disk element, a wide kneading disk element, and a progressive mixing screw element.

  The heating temperature at the time of melt kneading can be appropriately selected from the range of usually 180 to 360 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause opacity. Therefore, it is desirable to select a screw configuration that takes into account shearing heat generation and the like. Moreover, it is desirable to use an antioxidant or a heat stabilizer from the viewpoint of suppressing decomposition during kneading or molding in the subsequent process.

<Thermoforming>
The thermoforming conditions of the present invention can be appropriately determined according to the type of resin used and the molding method. Examples of thermoforming include insert molding, in-mold molding, and hot press.
Specific examples of the thermoforming method in the present invention will be described below, but it goes without saying that the present invention is not limited to the following.

The first embodiment of the thermoforming of the present invention is a method of insert molding by injecting a thermoplastic resin composition into a mold provided with an LDS additive-containing thermoplastic resin film.
In insert molding, a thermoplastic resin film containing an LDS additive is placed in advance in a cavity of a mold having a desired shape for injection molding, and a thermoplastic resin composition is injection molded (injection filling) into the outer space. Thus, a resin molded product is obtained. Furthermore, other layers such as an adhesive layer may be included. By performing the insert molding, it is possible to improve the strength of the resin molded product or to impart design properties. In this embodiment, the mechanical strength of the resin molded product obtained can be improved more by mix | blending inorganic fiber with a thermoplastic resin composition.
The injection molding temperature (resin temperature) in this embodiment is determined according to the type of thermoplastic resin contained in the thermoplastic resin composition. For example, when the thermoplastic resin is an amorphous resin, it is preferably (Tg) ° C. to (Tg + 150) ° C., and when the thermoplastic resin is a crystalline resin, it is preferably (resin melting point) ° C. to (resin melting point + 100) ° C. Tg is the glass transition temperature of the resin.
The mold temperature in this embodiment is determined according to the type of thermoplastic resin contained in the LDS additive-containing thermoplastic resin film. For example, in the case of an amorphous resin, (Tg-100) ° C. to Tg ° C. of the resin, and in the case of a crystalline resin, (load deflection temperature −200 measured at 0.45 MPa load according to ISO 75) ° C. to (ISO 75) A load deflection temperature of −50) ° C. measured with a 0.45 MPa load according to the above is preferred.
Further, it is preferable to apply pressure during the thermoforming, the pressure is preferably ^{100~1000kgf / cm 2, 200~800kgf / cm} 2 is more preferable.

The second embodiment of the present invention is a method for in-mold molding by injecting a thermoplastic resin composition into a mold provided with an LDS additive-containing thermoplastic resin film. Specifically, a sheet having an LDS additive-containing thermoplastic resin film in a desired shape is placed on a mold on a support, and a thermoplastic resin composition is injected to form a resin molded product and a plating layer This is a method of forming a processed portion that becomes a foundation for forming the. In this method, the LDS additive-containing thermoplastic resin film having a desired shape is separated from the sheet during or after molding, and only the LDS additive-containing resin film is transferred to the surface of the thermoplastic resin molded product. By setting it as the structure of this embodiment, the LDS additive containing resin film can be provided only on the part which forms the plating layer of the molded article derived from a thermoplastic resin composition.
In the sheet, the LDS additive-containing thermoplastic resin film is usually temporarily fixed on a support. Examples of the temporary fixing method include means by glue or heat. In the sheet, a release layer, a protective layer, or the like may be interposed between the support and the LDS additive-containing thermoplastic resin film.
The means for separating the LDS additive-containing thermoplastic resin film from the sheet during or after molding is not particularly defined, but as an example, the support is made larger than the mold cavity size. In addition, there is a method in which the sheet is partially sandwiched and fixed by a mold, and the LDS additive-containing resin film is peeled off after molding.
In this embodiment, the mechanical strength of the resin molded product obtained can be improved more by mix | blending inorganic fiber with a thermoplastic resin composition.
The injection molding temperature, mold temperature, and thermoforming pressure in this embodiment are the same as those in the first embodiment, and the preferred ranges are also the same.

The third embodiment of the present invention is a method of hot pressing an LDS additive-containing thermoplastic resin film and a thermoplastic resin film substantially free of an LDS additive. The thermoplastic resin film substantially free of LDS additive means, for example, that the content of LDS additive is 0.1% by weight of the resin component contained in the thermoplastic resin film substantially free of LDS additive. It means the following. According to the study by the inventors of the present application, it has been found that even if an LDS additive is added to a resin composition containing a flame retardant or a dye / pigment, a plating layer may not be formed successfully. The thermoplastic resin film substantially free of LDS additives can be blended with flame retardants and dyes and pigments, and the flame retardants and dyes and pigments can be added to thermoplastic resins without adversely affecting plating properties. It becomes possible to mix | blend with a film.
In this embodiment, the mechanical strength of the resin molded product (sheet) obtained can be further improved by blending inorganic fibers into the thermoplastic resin composition.
The heat pressing temperature in this case is a range of a glass transition point (Tg) of the resin in the case of an amorphous resin from −20 ° C. to Tg + 150 ° C., and a melting point of the resin in the range of −20 ° C. to 20 ° C. + 80 ° C. It is preferable that
Moreover, it is preferable to apply a pressure in the case of thermoforming, and as a pressure, 1-500 kgf / cm < ² > is preferable and 3-200 kgf / cm < ² > is more preferable.

  The resin molded product of the present invention is obtained by the method for producing a resin molded product of the present invention.

<Formation of plating layer>
The present invention further discloses a method for producing a resin molded product with a plated layer. The method for producing a resin molded product with a plating layer according to the present invention is such that the surface of the resin molded product produced by the method for producing a resin molded product according to the present invention is further irradiated with a laser and then a metal is applied to form a plating layer. Including doing.
The process of providing a plating layer on the surface of a resin molded product will be described with reference to FIG.
FIG. 1 is a schematic view showing a process of forming plating on the surface of a resin molded product 1 by a laser direct structuring technique. In FIG. 1, the resin molded product 1 is a flat substrate. However, the resin molded product 1 is not necessarily a flat substrate, and may be a resin molded product that is partially or entirely curved. Further, the resin molded product 1 is not limited to the final product, and includes various parts.
Next, in the method for producing a resin molded product with a plated layer of the present invention, the resin molded product 1 is irradiated with a laser 2.

  The laser 2 is not particularly limited, and can be appropriately selected from known lasers such as a YAG laser, an excimer laser, and electromagnetic radiation, and a YGA laser is particularly preferable. Further, the wavelength of the laser 2 is not particularly limited. The wavelength range of the preferable laser 2 is 200 nm to 1200 nm, and particularly preferably 800 to 1200 nm.

  When the laser 2 is irradiated onto the resin molded product 1, the resin molded product 1 is activated only in the portion 3 irradiated with the laser 2. The resin molded product 1 is applied to the plating solution 4 in the activated state. The plating solution 4 is not particularly defined, and a wide variety of known plating solutions can be used. A metal component in which copper, nickel, gold, silver, and palladium are mixed is preferable, and copper is more preferable.

  The method of applying the resin molded product 1 to the plating solution 4 is not particularly limited, and examples thereof include a method of adding the resin molded product 1 into a solution containing the plating solution. In the resin molded product 1 after application of the plating solution, the plated layer 5 is formed only in the portion irradiated with the laser 2 to obtain a resin molded product with a plated layer.

  In the method of the present invention, a circuit interval having a width of 1 mm or less and further 150 μm or less (the lower limit is not particularly defined, but for example, 30 μm or more) can be formed. Such a circuit is preferably used as an antenna of a portable electronic device component. That is, as an example of a preferred embodiment of the resin molded product 1 of the present invention, a resin molded product in which a plating layer provided on the surface of a portable electronic device component has performance as an antenna can be mentioned.

  In addition, within the range which does not deviate from the meaning of the present invention, JP2011-219620A, JP2011-195820A, JP2011-178873A, JP2011-168705A, JP2011-148267A. The description of the publication can be taken into consideration.

<Resin molded product with plating layer>
The resin molded product with a plated layer of the present invention is obtained by the method for producing a resin molded product with a plated layer of the present invention. The resin molded product with a plated layer of the present invention is preferably used for a portable electronic device component having an antenna. Examples of portable electronic device parts include internal structures and housings such as electronic notebooks, PDAs such as portable computers, pagers, mobile phones, and PHS. In particular, the resin molded product is suitable for a plate-shaped portable electronic device component having an average thickness excluding ribs of 1.2 mm or less (the lower limit is not particularly defined, for example, 0.4 mm or more). Particularly suitable as a housing.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Synthesis of polyamide resin MP6>
730 g of adipic acid was charged into a flask equipped with a stirrer, thermometer, reflux condenser, raw material dropping device, heating device, etc., and the temperature inside the flask was raised to 160 ° C. in a nitrogen atmosphere to melt adipic acid. . Into the flask, 680 g of mixed xylylenediamine containing 30 mol% of paraxylylenediamine and 70 mol% of metaxylylenediamine was successively added dropwise over about 2.5 hours. During this time, the reaction was continued with stirring while maintaining the internal temperature always above the melting point of the product, and the temperature was raised to 270 ° C. at the end of the reaction. Water generated by the reaction was discharged out of the reaction system by a partial condenser. After completion of the dropping, the reaction was continued with stirring at a temperature of 275 ° C., and the reaction was terminated after 1 hour. The product was removed from the flask, cooled with water and pelletized. The obtained polyamide resin had a melting point of 258 ° C. The relative viscosity was 2.1.

<LDS additive>
Black1G: Copper chromium oxide (CuCr ₂ O ₄ ) (manufactured by Shepherd Japan)
<Inorganic fiber>
03T-296GH: Glass fiber (Nippon Electric Glass)
<Talc>
Micron White 5000S (Made by Hayashi Kasei)
<Release agent>
CS8CP (Nitto Kasei Kogyo)

<Production of resin pellets>
Each component was weighed so as to have the composition shown in the table below, blended with a tumbler, except for glass fiber, charged from the root of a twin screw extruder (Toshiki Machine, TEM26SS), and melted. Later, the glass fiber was side-fed to produce a resin composition pellet. The temperature setting of the extruder was 280 ° C.

In the above table, each component indicates a weight ratio.

<Preparation of LDS additive-containing thermoplastic resin film>
Each component was weighed so as to have the composition shown in the following table, which will be described later, and a film was prepared with a short-axis extruder equipped with a 150-mm wide T-die. As film production conditions, a barrel temperature of 280 ° C., a die temperature of 280 ° C., and a roll temperature of 80 ° C. were obtained, and a film having a thickness of about 100 μm was obtained.

In the above table, each component indicates a weight ratio.

<Example 1 (insert molding)>
The LDS additive-containing thermoplastic resin film obtained above is placed in a 100 mold, and the resin pellet melt is injection molded and insert molded at a cylinder temperature of 300 ° C. and a mold temperature of 130 ° C. I got a product. It was found that the obtained resin molded product was excellent in adhesion because the part derived from the LDS additive-containing thermoplastic resin film and the part derived from the resin pellet were integrated. Also, the mechanical strength was excellent.

<Example 2 (in-mold molding)>
The LDS additive-containing thermoplastic resin film obtained above was cut into 10 cm × 10 cm, and a sheet temporarily fixed on the surface of a support (plastic film) larger than the mold was produced. The sheet was placed in a mold so that the LDS additive-containing thermoplastic resin film was placed in a desired position. At this time, a part of the support protruded from the mold, and the sheet was fixed by the mold. The resin pellet melt was injected at a cylinder temperature of 300 ° C. and a mold temperature of 130 ° C., and transferred in-mold to obtain a resin molded product. The obtained resin molded product is fused so that the part derived from the LDS additive-containing thermoplastic resin film is integrated at a desired position of the molded product derived from the resin pellet, and has excellent adhesion. I understood that. Also, the mechanical strength was excellent.

<Platting appearance (plating properties)>
Using a laser irradiation apparatus (manufactured by Trumpf, VMc1) (YAG laser maximum output 15 W at a wavelength of 1064 nm) in the range of 10 × 10 mm of the surface of the part derived from the LDS additive-containing thermoplastic resin film of the obtained resin molded product, output Irradiation was performed at 60%, a frequency of 100 kHz, and a speed of 4 m / s. The subsequent plating process was carried out in a 48 ° C. plating tank made of electroless Enthone and ENPLATE LDS CU 400 PC. The plating property was determined by visual observation of the thickness of copper plated for 20 minutes.
Evaluation was performed as follows. The results are shown in Table 3 below.
A: Good appearance (confirmed that the copper color is dark and the plating is thick)
B: Plating is on board but is slightly thin (not practical)

1 resin molded product, 2 laser, 3 laser irradiated part, 4 plating solution, 5 plating layer

Claims (8)

A method for producing a resin molded article, comprising: thermoforming a thermoplastic resin composition containing a thermoplastic resin and a laser direct structuring additive, and a thermoplastic resin of the same family as the thermoplastic resin. The method for producing a resin molded product according to claim 1, comprising injection-molding or in-mold molding the thermoplastic resin composition into a mold having the film disposed thereon. The manufacturing method of the resin molded product of Claim 1 or 2 with which the said thermoplastic resin composition contains an inorganic fiber. The manufacturing method of the resin molded product of Claim 3 whose said inorganic fiber is glass fiber. The manufacturing method of the resin molded product of any one of Claims 1-4 with which the said film and the said thermoplastic resin composition each contain a polyamide resin. It further includes applying a metal to the surface of the resin molded product manufactured by the method for manufacturing a resin molded product according to any one of claims 1 to 5 and then applying a metal to form a plating layer. The manufacturing method of the resin molded product with a plating layer. The manufacturing method of the resin molded product with a plating layer of Claim 6 with which the said plating layer contains copper. A resin molded product with a plated layer obtained by the method for producing a resin molded product with a plated layer according to claim 6 or 7.